CN105143336A - A composition, articles made therefrom, and method of making the articles - Google Patents

A composition, articles made therefrom, and method of making the articles Download PDF

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Publication number
CN105143336A
CN105143336A CN201380068547.9A CN201380068547A CN105143336A CN 105143336 A CN105143336 A CN 105143336A CN 201380068547 A CN201380068547 A CN 201380068547A CN 105143336 A CN105143336 A CN 105143336A
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cross
polyethylene
replacement scheme
weight
composition
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Inventor
D·常
C·贝克
J·周
S·格拉
J·科让
B·乔杜里
M·埃斯吉尔
S·森古普塔
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/244—Stepwise homogeneous crosslinking of one polymer with one crosslinking system, e.g. partial curing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

A crosslinked polyethylene composition formed through reaction of (A) functionalized polyethlyene having vinyltrialkoxysilanol grafted functionalities; and (B) hydroxyl-terminated silicone, wherein the crosslinked polyethylene comprises -C-C-Si-[O-Si(C)2]m-O-Si-C-C-crosslinkages is provided; and (C) a small amount of catalyst. Articles made from the crosslinked polyethtylene and methods of making such articles are also provided.

Description

A kind of composition, the article manufactured by it and manufacture the method for described article
Technical field
The present invention relates to a kind of composition, the article manufactured by it and a kind of method manufacturing described article.
Background technology
Crosslinked polyethylene (PEX) is applied for multiple end-use, and PEX pipeline is the one in most most common use.PEX pipeline represents superior heat resistance, is particularly suitable for the application of hot and cold pipe fitting.The ducted cross-link bond of PEX-b is formed by the silanol condensation between the grafting vinyl Trimethoxy silane functional group of two on polyethylene, is thus connected Polyethylene Chain.Partial cross-linked polyethylene produces higher molecular weight, and therefore for comparatively posted sides pipeline, produces viscosity higher and melt strength.Manufacturing the complicacy of PEX-b pipeline and cost results from for crosslinked needs humidity activated after at high temperature carrying out extruding, and describedly crosslinkedly may need to be exposed to heat and humidity several days at the most in some conditions.
Summary of the invention
The present invention is a kind of composition, the article manufactured by it and a kind of method manufacturing described article.
In one embodiment, the invention provides a kind of cross-linked polyethylene composition, its functional polyethylene by making (A) have vinyl trialkyl oxysilane alcohol grafted functional group; (B) hydroxy-end capped silicone; (C) a small amount of catalyst reaction and being formed, wherein said crosslinked polyethylene comprises C-C-Si-[O-Si (C) 2] m-O-Si-C-C cross-link bond.
Embodiment
The present invention is a kind of composition, article manufactured by it and manufacture the method for described article.
Composition according to the present invention is a kind of cross-linked polyethylene composition, its functional polyethylene by making (A) have vinyl trialkyl oxysilane alcohol grafted functional group; (B) one or more hydroxy-end capped silicone; (C) a small amount of catalyst reaction and being formed, wherein said crosslinked polyethylene comprises-C-C-Si-[O-Si (C) 2] m-O-Si-C-C-cross-link bond.
In an alternative embodiment, the present invention further provides a kind of method preparing cross-linked polyethylene resin, it comprises the polyethylene providing and have vinyl trialkyl oxysilane alcohol grafted functional group; Mix with by silicone hydroxy-end capped to described polyethylene and one or more, to form cross-linkable mixtures; Wherein said cross-linkable mixtures can form-C-C-Si-[O-Si (C) at lower than the temperature of 70 DEG C 2] m-O-Si-C-C-cross-link bond.
In another alternate embodiment, the present invention further provides a kind of article, it comprises the crosslinked polyethylene according to any one in embodiment disclosed herein.
In another alternate embodiment, the present invention further provides a kind of method manufacturing article, it is comprised to be selected from by one or more and transforms according to the cross-linked polyethylene composition of any one in embodiment disclosed herein by the processing technology of the following group formed: injection-molded, extruding, compression molded, roational molding, thermoforming, blown-moulding, powder coating, Banbury (Banbury) batch mixer, fiber sprinning and calendering.
The exemplary vinyl trialkyl oxysilane alcohol functional group be applicable in embodiments of the invention comprises vinyltrimethoxy silane alcohol, vinyltriethoxysilane alcohol, vinyl tripropoxy silanol, vinyl three pentyloxy silanol and the combination of person both it or more.
Crosslinked polyethylene comprises-C-C-Si-[O-Si (C) 2] m-O-Si-C-C-cross-link bond, wherein m is any integer of 1 or larger.Comprise herein and disclose all indivedual values and subrange herein; For example, the value of m can be equal to or greater than 1 any integer, or in replacement scheme, the value of m can be equal to or greater than 2 any integer, or in replacement scheme, the value of m can be equal to or greater than 3 any integer, or in replacement scheme, the value of m can be equal to or greater than 4 any integer, or in replacement scheme, the value of m can be equal to or greater than 5 any integer.
One or more hydroxy-end capped silicone be applicable in embodiments of the invention has following formula usually:
Wherein R 1and R 2it is the alkyl with at least one carbon.N to be value be at least 1 any integer.Comprise herein and disclose all indivedual values and subrange herein; For example, the value of n can be equal to or greater than 1 any integer, or in replacement scheme, the value of n can be equal to or greater than 2 any integer, or in replacement scheme, the value of n can be equal to or greater than 3 any integer, or in replacement scheme, the value of n can be equal to or greater than 4 any integer, or in replacement scheme, the value of n can be equal to or greater than 5 any integer.
Cross-linkable mixtures can form-C-C-Si-[O-Si (C) at less than or equal to the temperature of 70 DEG C 2] m-O-Si-C-C-cross-link bond.Comprise herein and all indivedual value of the open temperature less than or equal to 70 DEG C and subrange herein.For example, cross-linkable mixtures may can form cross-link bond at less than or equal to the temperature of 70 DEG C, or in replacement scheme, cross-linkable mixtures may can form cross-link bond at less than or equal to the temperature of 60 DEG C, or in replacement scheme, cross-linkable mixtures may can form cross-link bond at less than or equal to the temperature of 50 DEG C, or in replacement scheme, cross-linkable mixtures may can form cross-link bond at less than or equal to the temperature of 40 DEG C, or in replacement scheme, cross-linkable mixtures may can form cross-link bond at less than or equal to the temperature of 30 DEG C.
In an alternative embodiment, the article the invention provides a kind of composition according to any one in previous embodiment, manufacture its method, being manufactured by it and the method manufacturing described article, difference is, cross-linkable mixtures can form C-C-Si-[O-Si (C) at the temperature of 10 to 70 DEG C 2] m-O-Si-C-C cross-link bond.Comprise herein and disclose all indivedual value and the subrange of 10 to 70 DEG C herein.For example, cross-linkable mixtures can at 10 to 70 DEG C or in replacement scheme 10 to 50 DEG C or in replacement scheme 15 to 30 DEG C or in replacement scheme 25 to 35 DEG C or in replacement scheme 10 to 50 DEG C or in replacement scheme 20 to 50 DEG C or form C-C-Si-[O-Si (C) at the temperature of 20 to 30 DEG C in replacement scheme 2] m-O-Si-C-C cross-link bond.
In an alternative embodiment, the article the invention provides a kind of composition according to any embodiment disclosed herein, manufacture its method, being manufactured by it and the method manufacturing described article, difference is, polyethylene and 50ppm mix to form crosslinked polyethylene to 20 % by weight hydroxy-end capped silicone.Comprise herein and the openly all indivedual value of 50ppm to 20 % by weight and subrange herein; For example, the amount of hydroxy-end capped silicone can from 50ppm, 100ppm, 500ppm, be limited to for 0.1 % by weight, 0.5 % by weight, 1.5 % by weight, 2.5 % by weight, 3.5 % by weight or 4.5 % by weight 100ppm, 200ppm, 600ppm, 0.2 % by weight, 0.5 % by weight, 3.6 % by weight, 5 % by weight, 8.5 % by weight, 15 % by weight, the upper limit of 18 % by weight or 20 % by weight.For example, the amount of hydroxy-end capped silicone can at 50ppm in 20 % by weight scopes, or in replacement scheme, the amount of hydroxy-end capped silicone can at 100ppm in 10 % by weight scopes, or in replacement scheme, the amount of hydroxy-end capped silicone can at 1000ppm in 5 % by weight scopes, or in replacement scheme, the amount of hydroxy-end capped silicone can at 100ppm in 5 % by weight scopes.
In yet another embodiment, the article the invention provides a kind of composition according to any embodiment disclosed herein, manufacture its method, being manufactured by it and the method manufacturing described article, difference is, the viscosity of crosslinked polyethylene at 190 DEG C is at least 10 7pas.For example, the viscosity of crosslinked polyethylene at 190 DEG C can be at least 10 7pas, or be at least 10 in replacement scheme 8pas, or be at least 10 in replacement scheme 9pas, or be at least 10 in replacement scheme 10pas.
Do not wish fettered by any concrete theory, according to believing, increasing hydroxy-end capped silicone amount increases causing the viscosity of composition.
In yet another embodiment, the invention provides a kind of composition according to any embodiment disclosed herein, the article manufactured by it and manufacture the method for described article, difference is, polyethylene is selected from the one or many person by the following group formed: Low Density Polyethylene, high density polyethylene(HDPE), linear low density polyethylene and its combination.
In yet another embodiment, the invention provides a kind of composition according to any embodiment disclosed herein, the article manufactured by it and manufacture the method for described article, difference is, polyethylene is selected from the one or many person by the following group formed: Alathon or ethylene/alpha-olefin interpolymers.
As used herein, term " interpretation " refers to by making at least two kinds of dissimilar monomer polymerizations and the polymkeric substance prepared.Therefore, generic term interpretation comprises multipolymer (usually in order to refer to the polymkeric substance prepared by two kinds of dissimilar monomers) and by the polymkeric substance prepared more than two kinds of dissimilar monomers.
In yet another embodiment, the article the invention provides a kind of composition according to any embodiment disclosed herein, manufacture its method, being manufactured by it and the method manufacturing described article, difference is, poly density is 0.925 to 0.97g/cm 3.Comprise herein and disclose 0.925 to 0.97g/cm herein 3all indivedual value and subrange; For example, the density of density of pe can from 0.925,0.930,0.930,0.935,0.940,0.945,0.950,0.955 or 0.965g/cm 3under be limited to 0.930,0.930,0.935,0.940,0.945,0.950,0.955,0.960 or 0.97g/cm 3the upper limit scope in.For example, the density of density of pe can be 0.925 to 0.97g/cm 3, or in replacement scheme, the density of density of pe can be 0.940 to 0.950g/cm 3, or in replacement scheme, the density of density of pe can be 0.925 to 0.940g/cm 3, or in replacement scheme, the density of density of pe can be 0.925 to 0.935g/cm 3, or in replacement scheme, the density of density of pe can be 0.935 to 0.945g/cm 3.
In yet another embodiment, the article the invention provides a kind of composition according to any embodiment disclosed herein, manufacture its method, being manufactured by it and the method manufacturing described article, difference is, poly I 20.001 to 100g/10min.Comprise herein and disclose all indivedual value and the subrange that 0.001 arrives 100g/10min; For example, polyethylene I 2can in the scope of the upper limit being limited to 0.006,0.05,2,5,10,50 or 100g/10min under 0.001,0.005,0.01,1,2,3,4,5,10,20,50 or 90g/10min.For example, poly I 2can arrive within the scope of 10g/10min 0.01, or in replacement scheme, poly I 2can arrive within the scope of 5g/10min 0.01, or in replacement scheme, poly I 2can arrive within the scope of 5g/10min 0.05, or in replacement scheme, poly I 2can arrive within the scope of 10g/10min 1, or in replacement scheme, poly I 2can within the scope of 0.05 to 1g/10min.
In yet another embodiment, the article the invention provides a kind of composition according to any embodiment disclosed herein, manufacture its method, being manufactured by it and the method manufacturing described article are according to any embodiment difference disclosed herein, and polyethylene is that density is equal to or greater than 0.940 to 0.97g/cm 3high density polyethylene(HDPE).Comprise herein and disclose 0.940 to 0.97g/cm herein 3all indivedual value and subrange; For example, the density of high density polyethylene(HDPE) can be from 0.940,0.945,0.950,0.955 or 0.965g/cm 3under be limited to 0.945,0.950,0.955,0.960 or 0.97g/cm 3the upper limit.For example, density can 0.940 to 0.97g/cm 3in scope, or in replacement scheme, density can 0.940 to 0.955g/cm 3in scope, or in replacement scheme, density can 0.945 to 0.950g/cm 3in scope, or in replacement scheme, density can 0.950 to 0.960g/cm 3in scope.
High density ethylene polymer component can be prepared by synthesis as known in the art, and described synthesis includes but not limited to the vapour phase polymerization using chromium-based catalysts system.
Ethylene/alpha-olefin interpolymers can use any conventional ethylene/alpha-olefine polymerizing technology generally known in this area to manufacture.For example, the polymerization of ethylene/alpha-olefin interpretation can realize about under the condition known by Z-N (Ziegler-Natta) or Kaminski-Xin (Kaminsky-Sinn) type polyreaction in the art.Ethylene/alpha-olefin interpolymers can also use list or bicyclic pentadiene, indenyl or fluorenyl transition metal (preferably 4 races) catalyzer or constrained geometry catalyst to manufacture.If desired, suspension, solution, slurries, gas phase, solid state powder polymerization or other processing condition can be adopted.If desired, carrier can also be adopted, such as silicon-dioxide, aluminum oxide or polymkeric substance (such as tetrafluoroethylene or polyolefine).
Ethene can also be selected from by the alkene system polymerization of unsaturated monomers of the following group formed with at least one: C3-C12 alpha-olefin; The C1-C12 alkyl ester of C3-C20 monocarboxylic acid; Mono-or the dicarboxylic acid of unsaturated C3-C20; The acid anhydrides of unsaturated C4-C8 dicarboxylic acid; With the vinyl ester of saturated C2-C18 carboxylic acid.
Polyethylene can pass through free radical technique, Ziegler-Natta catalyst system (such as United States Patent (USP) the 4th, 661, No. 465 and the 4th, what present in 873, No. 300 improves one's methods), metallocene catalytic system and/or constrained geometry catalyst system (such as United States Patent (USP) the 5th, 272, No. 236 and the 5th, disclosed those in 278, No. 272) to prepare, the mode that described patent is quoted separately is in full incorporated herein.
High density polyethylene(HDPE) can comprise one or more alpha-olefin comonomer of any amount; For example, high density polyethylene(HDPE) can comprise one or more alpha-olefin comonomer being about less than 15 % by weight with the weighing scale of high density polyethylene(HDPE).Comprise herein and be openly less than herein 15 % by weight all indivedual value and subrange; For example, % by weight of one or more alpha-olefin comonomer can be limited to from 0,1,2,3,5,7,9,12 or 14 % by weight 5,9,10,12 or 15 % by weight the upper limit.For example, high density polyethylene(HDPE) can comprise one or more alpha-olefin comonomer being about less than 10 % by weight with the weighing scale of high density polyethylene(HDPE); Or in replacement scheme, high density polyethylene(HDPE) can comprise one or more alpha-olefin comonomer being about less than 7 % by weight with the weighing scale of high density polyethylene(HDPE); In replacement scheme, high density polyethylene(HDPE) can comprise one or more alpha-olefin comonomer being about less than 5 % by weight with the weighing scale of high density polyethylene(HDPE).
High density polyethylene(HDPE) can comprise the ethene of any amount; For example, high density polyethylene(HDPE) can comprise the ethene of about at least 85 % by weight with the weighing scale of high density polyethylene(HDPE).Comprise herein and be openly equal to or greater than herein 85 % by weight all indivedual value and subrange; For example, % by weight of ethene can be limited to from 85,87,88,90,91,95,98 or 99 % by weight 90,91,93,95,98 or 100 % by weight the upper limit.For example, high density polyethylene(HDPE) can comprise the ethene of at least 85 % by weight with the weighing scale of high density polyethylene(HDPE); Or in replacement scheme, high density polyethylene(HDPE) can comprise the ethene of at least 90 % by weight with the weighing scale of high density polyethylene(HDPE); In replacement scheme, high density polyethylene(HDPE) can comprise the ethene of at least 95 % by weight with the weighing scale of high density polyethylene(HDPE).
Alpha-olefin comonomer typically has and is no more than 20 carbon atoms.For example, alpha-olefin comonomer can preferably have 3 to 10 carbon atoms, and more preferably has 3 to 8 carbon atoms.Exemplary alpha-olefin comonomer includes, but is not limited to propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 4-methyl-1-pentene.Alpha-olefin comonomer can preferably be selected from by the following group formed: propylene, 1-butylene, 1-hexene and 1-octene, and is more preferably selected from by the following group formed: 1-hexene and 1-octene.
Any conventional ethylene homopolymerization or copolyreaction can in order to manufacture high-density polyethylene olefinic constituent of the present invention.Described conventional ethylene homopolymerization or copolyreaction include, but is not limited to the combination of vapour phase polymerization, slurry phase polymerization, liquid polymerization and its series connection or parallel use conventional reactor (such as Gas-phase reactor, loop reactor, stirred tank reactor, batch reactor and its combination).
In yet another embodiment, the invention provides a kind of composition according to any embodiment disclosed herein, the article manufactured by it and manufacture the method for described article, difference is, the melting index (I of high density polyethylene(HDPE) 21); For example, the melting index (I of high-density polyethylene composition 21) can within the scope of 0.1 to 200g/10min.Comprise herein and disclose all indivedual value and the subrange that 0.1 arrives 200g/10min herein; For example, the melting index (I of high-density polyethylene composition 21) can arrive within the scope of 10g/10min 0.1, or in replacement scheme, the melting index (I of high-density polyethylene composition 21) can arrive within the scope of 5g/10min 1, or in replacement scheme, the melting index (I of high-density polyethylene composition 21) can within the scope of 0.5 to 15g/10min.
In yet another embodiment, the invention provides a kind of composition according to any embodiment disclosed herein, the article manufactured by it and manufacture the method for described article, difference is, the molecular weight distribution of high density polyethylene(HDPE) is in 3 to 50 scopes.Comprise herein and disclose herein 3 to 50 all indivedual value and subrange; For example, the molecular weight distribution of high-density polyethylene composition can be limited to the upper limit of 3,15,25,35,45 or 50 from 3,10,20,30 or 40.For example, the molecular weight distribution of high density polyethylene(HDPE) can in 3 to 50 scopes, or in replacement scheme, the molecular weight distribution of high density polyethylene(HDPE) can in 3 to 25 scopes, or in replacement scheme, the molecular weight distribution of high density polyethylene(HDPE) can in 10 to 30 scopes, or in replacement scheme, the molecular weight distribution of high density polyethylene(HDPE) can in 3 to 50 scopes, or in replacement scheme, in 25 to 50 scopes.As used herein, term molecular weight distribution or " MWD " refer to the weight average molecular weight (Mw) that hereinafter the describes in further detail ratio than number average molecular weight (Mn), i.e. (Mw/Mn).
Cross-linked polyethylene composition may further include additional additive.Described additive comprises (but being not limited to) static inhibitor, toner, dyestuff, lubricant, weighting agent, pigment, main anti-oxidant, secondary antioxidant, processing aid, UV stablizer and its combination.Cross-linked polyethylene composition can contain the additive of any amount.Cross-linked polyethylene composition can comprise in the weighing scale of total polyethylene composition with the additive of combination weight about 0 to about 2%.Comprise herein and herein open about 0 to about 2 % by weight all indivedual value and subrange; For example, total polyethylene composition can comprise additive with combination weight 0 to 0.8% in the weighing scale of cross-linked polyethylene composition.Antioxidant, such as IRGANOX1076 and IRGANOX1010 is conventional to protect polymkeric substance to avoid heat and/or oxidative degradation.IRGANOX1076 and IRGANOX1010 is commercially available from BASF (BASF).
The high density polyethylene(HDPE) be applicable in the present invention can manufacture according to any technique as known in the art.
In a preferred embodiment, the present invention is a kind of goods, and it is prepared by crosslinkable polymeric composition.Multiple processing technology can in order to prepare article.The technique of particularly suitable comprises injection-molded, extruding, roational molding, thermoforming, blown-moulding, Banbury batch mixing tank and calendering.
The goods be applicable to comprise wire cable insulating, electric wire semiconduction article, electric wire and cable jacket, cable fitting, sole, polycomponent sole (comprising the polymkeric substance of different densities and type), packing ring, section bar, dutiable goods, building panel, matrix material (such as, Wood composite material), pipeline, foam, blown film and fiber (comprising binder fibre and spandex fiber).
In a specific embodiment, goods are pipelines of wall thickness 20cm at the most.Comprise herein and all indivedual value of open 20cm at the most and subrange.For example, the thickness of pipeline can be 20cm at the most, or in replacement scheme, and the thickness of pipeline can be 15cm at the most, or in replacement scheme, and the thickness of pipeline can be 12cm at the most, or in replacement scheme, and the thickness of pipeline can be 10cm at the most.
In yet another embodiment, the article the invention provides a kind of composition according to any embodiment disclosed herein, manufacture its method, being manufactured by it and the method manufacturing described article, difference is, a kind of method preparing cross-linked polyethylene resin is made up of following substantially: provide the polyethylene with vinyl trialkyl oxysilane alcohol grafted functional group; With by described polyethylene and one or more hydroxy-end capped silicone and optionally a small amount of catalyst mix, to form cross-linkable mixtures; Wherein said cross-linkable mixtures can form-C-C-Si-[O-Si (C) at lower than the temperature of 70 DEG C 2] m-O-Si-C-C-cross-link bond.
In yet another embodiment, the article the invention provides a kind of composition according to any embodiment disclosed herein, manufacture its method, being manufactured by it and the method manufacturing described article, difference is, cross-linked polyethylene composition is by making substantially to be formed by the following mixture reaction that forms: (A) has the functional polyethylene of vinyl trialkyl oxysilane alcohol grafted functional group; (B) one or more hydroxy-end capped silicone; (C) a small amount of catalyzer, wherein said crosslinked polyethylene comprises-C-C-Si-[O-Si (C) 2] m-O-Si-C-C-cross-link bond.
Testing method
Testing method comprises following:
According to ASTMD792, method B, measuring density in Virahol.
At 190 DEG C and respectively, under 2.16kg and 21.6kg load, melting index (I is measured according to ASTMD-1238 2and I 21).According to ASTM-D1238, condition 190 DEG C/10kg measures melt flow rate (MFR) (I 10).
Use and can be purchased and trade name Gao Tefu Roy can rise this (GoettfertRheotens) and be purchased melt strength tester from Gao Tefu company (GottfertInc.) from the associating of the capillary rheometer of Instron Corporation (InstronCorporation) by trade name Instron kapillary model 3211 (InstronCapillaryModel3211), measure Gao Tefu (Gottfert) or Roy rises (Rheoten) melt strength.Capillary rheometer is in order to pass through mould by polymer melt with constant output capacity.Melt strength tester is in order to the molten polymer long filament that extends with using roll single shaft.

Claims (10)

1. a cross-linked polyethylene composition, its functional polyethylene by making (A) have vinyl trialkyl oxysilane alcohol grafted functional group; (B) hydroxy-end capped silicone; (C) a small amount of catalyst reaction and being formed, wherein said crosslinked polyethylene comprises-C-C-Si-[O-Si (C) 2] m-O-Si-C-C-cross-link bond.
2. crosslinked polyethylene according to claim 1, the amount of the hydroxy-end capped silicone in wherein said reaction is that 50ppm is to 20% with the poly gauge in described reaction.
3. crosslinked polyethylene according to claim 1, its viscosity at 190 DEG C is at least 10 7pa.s.
4. prepare a method for cross-linked polyethylene composition, it comprises
The polyethylene with vinyl trialkyl oxysilane alcohol grafted functional group is provided; With
Described polyethylene is mixed, to form crosslinkable resin to 20% hydroxy-end capped silicone with poly gauge 50ppm;
Wherein said cross-linkable mixtures can form-C-C-Si-[O-Si (C) at lower than the temperature of 70 DEG C 2] m-O-Si-C-C-cross-link bond.
5. goods, it comprises the cross-linked polyethylene composition according to any one of claim 1 to 4.
6. goods according to claim 5, wherein said article are pipelines.
7. pipeline according to claim 6, its wall thickness is 20cm at the most.
8. pipeline according to claim 7, wherein said pipeline is extruding.
9. manufacture a method for pipeline, it comprises the step of the cross-linked polyethylene composition of extruding according to any one of Claim 1-3.
10. the cross-linked polyethylene composition according to any one of Claim 1-3, wherein said crosslinked polyethylene represents at least 10 at 190 DEG C 7the viscosity of Pas.
CN201380068547.9A 2012-12-31 2013-11-19 A composition, articles made therefrom, and method of making the articles Pending CN105143336A (en)

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Application publication date: 20151209